Polymerization products and process of making same



Patented July 20, 1937 UNITED STATES PATENT OFFICE POLYMERIZATION PRODUCTS AND PROC- ESS OF MAKING SAME William Chalmers, Vancouver, British Columbia, Canada, assignor, by mesne assignments, to Riihm & Haas Company, Philadelphia, Pa.

No Drawing.

Continuation of application Se- 18 Claims.

This invention relates to the preparation of polymerization products of derivatives of methacrylic acid such as methacrylic ethyl ester and. methacrylic nitrile.

Substances produced by polymerization of methacrylic ethyl ester and methacrylic nitrile may be used as artificial resins, transparent or glass-like resins, or as plastic materials.

The polymerization products of methacrylic ethyl ester are obtained by exposing the methacrylic ethyl ester to the action of heat, sunlight, or ultra-violet light, with or without the use of catalysts, such as sodium, potassium, benzoyl peroxide or other organic or inorganic peroxides. The ester may be in the pure state or in solution in solvents such as benzene.

' While the polymerization may be completed by allowing the ester to stand in the dark in a warm place for several weeks, it is preferred to 20 subject the ester to the action of the agents above mentioned in order to accelerate the rate of polymerization so that the polymerization products may be produced on a commercial scale.

The nature of the product resulting from polymerization of methacrylic ester varies from that of an elastic solid to a hard glassy substance, dependent upon the duration or completeness of the polymerization process. The elastic substance thus obtained may be converted into the hard glassy form by distilling off the unchanged monomer at 130 C.

Both forms of the polymerization product thus obtained are soluble in all common organic solvents, except the alcohols in which they are only partially soluble. Solution of the polymer is rather slow and swelling first takes place followed by solution of the swollen mass. The

. elastic substance or product obtained is simply the glassy form which has been swollen by means of the unchanged monomer and, because of this previous swelling, is more quickly soluble in organic solvents.

These polymerized substances, when allowed to evaporate on a glass, metal or wood surface, form a smooth glassy coating of great durability and are thus particularly suited as a base for lacquers.

The methacrylic nitrile may be polymerized by the application of heat or by allowing the nitrile to stand with alkali metals such as those referred to in connection with the polymerization of the methacrylic ethyl ester.

The monomeric ester or nitrile may be hydrolyzed before polymerization by means of dilute acids or alkalies to give the methacrylic acid which is already known to polymerize to a porcelain-like mass.

In order to more clearly illustrate the manner in which the polymerization process above described may be carried out, the following ex- 5 amples are given:

Example 1 Methacrylic ethyl ester, to which about onehalf of one per cent of benzoyl peroxide has been added, is placed in a suitable quartz or other container and exposed to the radiation from a mercury vapor lamp. The rate of polymerization depends, of course, upon temperature conditions and upon the intensity of the radiation. 15 It has been found that when a small sample of the ester and peroxide is placed in close proximity to a small volt lamp the ester is converted into a glassy solid material in a period of time ranging from one and one-quarter to one and one-half hours.

Example 2 The methacrylic ethyl ester may be heated in a closed container for sixteen to twenty hours at C. at the end of which time it is converted into the solid polymer. This solid may be dissolved in all of the common organic solvents except the alcohols in which it is only partially soluble.

Ezvample 3 Methacrylic nitrile is treated by placing therein one per cent of sodium wire and allowing the nitrile to stand for a week, at the end of which time it is entirely converted into a solid resinous mass of a dark brown color. The sodium is destroyed and the dark color removed by the addition of alcohol. The purification may then be completed by washing with water so that the final product is a light colored resinous material.

Example 4 nitrile can be utilized as a plastic material ior various purp ses.

This application is a continuation oi my copending application Serial No. 431,982, flied February 27, 1930.

I claim:

1. A composition oi matter comprising a polymer oi the butyl ester oi a-methacrylic. acid.

2. A composition oi matter comprising polymeric butyl-a-methacrylate.

3. A composition oi matter comprising a polymer oi the nitrile oi m-methacrylic acid.

4. A composition oi matter comprising polymeric a-methacrylic nitrile.

5. The process oi preparing polymerized butyla-methacryiate which comprises subjecting butyl-a-methacrylate to polymerizing influences in the presence oi an oxygen-yielding substance.

6. The process oi preparing polymerized butyl-a-methacrylate which comprises subjecting butyl-a-methacrylate to polymerizing influences in the presence oi an organic peroxide.

7. The process oi preparing polymerized butyl-e-methacrylate which comprises heating butyl-a-methacrylate in the presence oi benzoyl peroxide.

8. The process oi preparing polymerized a- 'methacrylic nitrile which comprises subjecting a-methacrylic nitrile to polymerizing influences in the presence oi an oxygen-yielding substance.

9. The process of preparing polymerized amethacrylic nitrile which comprises subjecting s-methacrylic nitrile to polymerizing influences in the presence of an organic peroxide.

10. The process of preparing polymerized amethacrylic nitrile which comprises heating 1:-

methacrylic nitrile in the presence oi benzoyl peroxide.

11. The process oi preparing polymerized ethyl s-methacrylate which comprises subjecting ethyl a-methacrylate to polymerizing influences in the presence oi an oxygen yielding substance.

12. The process of preparing polymerized ethyl s-methacrylate which comprises subjecting ethyl a-methacrylate to polymerizing influences in the presence oi an organic peroxide.

13. The process oi preparing polymerized ethyl s-methacrylate which comprises heating ethyl s-methacrylate in the presence oi benzoyl peroxide.

14. The process oi polymerizing a member of the group consisting oi the ester and nitrile derivatives oi a-methacrylic acid, which comprises subjecting a member oi said group to polymerizing influences in the presence of an oxygen yielding substance.

15. The process oi polymerizing a member oi the group consisting oi the ester and nitrile derivatives of a-methacrylic acid, which comprises subjecting a member oi said group to polymerizing influences in the presence oi an organic peroxide.

16. The process oi polymerizing an ester oi amethacrylic acid which comprises heating said ester in the presence oi benzoyl peroxide.

17. A process which comprises polymerizing 

